Surface active agent and method of preparing the same

ABSTRACT

A NOVEL SURFACE ACTIVE AGENT COMPRISING A PHOSPHOROUS TRIESTER-TYPE COMPOUND HAVING THE FOLLOWING FORMULA:   R1-O-P(-O-R2)-O-R3   WHEREIN R1 IS A CONVENTIONAL NONIONIC SURFACE ACTIVE AGENT RESIDUE TO WHICH ETHYLENE OXIDE OR BOTH ETHYLENE OXIDE AND PROPYLENE OXIDE IS ADDED AND R2 AND R3 ARE TO CONVENTIONAL NONIOONIC SURFACE ACTIVE AGENY RESIDUE TO WHICH ETHYLENE OXIDE OR BOTH ETHYLENE OXIDE AND PROPYLENE OXIDE IS ADDED OR AN ALKYL GROUP HAVING 8 TO 22 CARBON ATOMS AND ITS PREPAATION ARE DESCRIBED. THE SURFACE ACTIVE AGENT IS SUPERIOR IN SURFACE ACTIVITY HEAT RESISTING STABILITY AND A REDUCED FOAMING PROPERTY.

United States Patent US. Cl. 260-403 Claims ABSTRACT OF THE DISCLOSURE Anovel surface active agent comprisin a phosphorous triester-typecompound having the following formula:

wherein R is a conventional nonionic surface active agent residue towhich ethylene oxide or both ethylene oxide and propylene oxide isadded, and R and R are a con ventional nonionic surface active agentresidue to which ethylene oxide or both ethylene oxide and propyleneoxide is added or an alkyl group having 8 to 22 carbon atoms and itspreparation are described. The surface active agent is superior insurface activity, heat-resisting stability and a reduced foamingproperty.

This invention relates to a novel surface active agent and a method ofpreparing the same.

An object of the present invention is to provide a novel surface activeagent which has superior surface activities, a heat-resisting stabilityand a reduced foaming property.

Other objects and advantages of the present invention will becomeapparent from the following description.

The surface active agent of the present invention comprises a compoundhaving the following general formula:

wherein R is a conventional nonionic surface active agent residue towhich one or more moles of ethylene oxide or one or more moles of bothethylene oxide and propylene oxide is added, and R and R are a memberselected from the group consisting of a conventional nonionic surfaceactive agent residue to which one or more moles of ethylene oxide or oneor more moles of both ethylene oxide and propylene oxide is added and analkyl group having 8 to 22 carbon atoms.

The above conventional nonionic surface active agent includes, forexample, (1) a nonionic surface active agent of such a type as anaddition product of l to 100 moles of ethylene oxide or 1 to 100 molesof both ethylene oxide and propylene oxide to one mole of higher alcoholhaving 8 to 22 carbon atoms such as octyl alcohol, lauryl alcohol,coconut alcohol, cetyl alcohol, stearyl alcohol, oleyl alcop CC hol,tridecyl alchol, etc.; (2) that of such a type as an addition product of1 to moles of ethylene oxide or 1 to 100 moles of both ethylene oxideand propylene oxide to one mole of alkyl phenol containing an alkylgroup having 4 to 22 carbon atoms such as butyl phenol, octyl phenol,nonyl phenol, dodecyl phenol, dinonyl phenol, etc.; (3) that of such atype as an addition product of 1 to 100 moles of ethylene oxide or 1 to100 moles of both ethylene oxide and propylene oxide to one mole ofhigher fatty acid having 8 to 22 carbon atoms such as coconut fattyacid, lauric acid, oleic acid, stearic acid, palmitic acid, etc.; (4)that of such a type as an addition product of 1 to 100 moles of ethyleneoxide or 1 to 100 moles of both ethylene oxide and propylene oxide toone mole of alkyl amine having 8 to 22 carbon atoms such as coconutamine, lauryl amine, stearyl amine, hexadecyl amine, etc.; (5) that ofsuch a type as an addition product of 1 to 100 moles of ethylene oxideor 1 to 100 moles of both ethylene oxide and propylene oxide to one moleof higher fatty acid amide having 8 to 22 carbon atoms such as lauricacid amide, stearic acid amide, palmitic acid amide, oleic acid amide,etc., and (6) that of such a type as an addition product of 1 to 100moles of ethylene oxide or 1 to 100 moles of both ethylene oxide andpropylene oxide to one mole of aryl phenol having 2 to 5 benzene ringssuch as p-phenyl phenol, benzyl naphthol and tri-ethylbenzene phenol,etc.

The surface active agent of the present invention is prepared by thefollowing method:

The compound wherein all of R R and R in the above formula areconventional surface active agent residues, is prepared by reacting onemole of triaryl phosphite or trichloroaryl phosphite with at least about3 moles of a conventional surface active agent using a strong basiccatalyst, which results in ester interchange of the former with thelatter.

The compound wherein one or two of R and R in the formula are alkylgroups having 8 to 22 carbon atoms, is prepared by reacting one mole oftriaryl phosphite or trichloroaryl phosphite with at least about threemoles of both conventional surface active agent and higher alcohol,wherein the mole ratio of the surface active agent to the higher alcoholis approximately /2 to 2, using a strong basic catalyst.

A strong basic catalyst, which is used in the present invention,includes, for example, metal alcoholates such as sodium methylate,potassium phenolate, etc.; quaternary ammonium hydroxides; inorgamcstrong bases such as sodium hydroxide, potassium hydroxide, etc; andalkali metals such as sodium, potassium, etc. As to the proportion ofthe basic catalyst, from 0.001 to 0.20 mole based on the moles oftriaryl phosphite or trichloroaryl phosphite is preferable.

Triaryl phosphite or trichloroaryl phosphite, which is used in thepresent invention, includes, for example, triphenyl phosphite,tri-p-cresyl phosphite, tri-o-cresyl phosphite, tri-m-cresyl phosphite,tri-butylphenyl phosphite, tri-o-chlorophenyl phosphite,tri-p-chlorophenyl phosphite, tri-m-chlorophenyl phosphite, etc.

Conventional surface active agents, which are used in the presentinvention, are listed hereinbefore.

The higher alcohol, which is used in the present invention, is asaturated or unsaturated alcohol containing an 3 alkyl group having 8 to22 carbon atoms which includes, for example, octanol, decanol, laurylalcohol, myristyl alcohol, palmityl alcohol, cetyl alcohol, stearylalcohol, oleyl alcohol, coconut alcohol, tridecyl alcohol, etc.

The ester interchange reaction of the present invention is effected at atemperature of 100 to 250 C. under atmospheric or reduced pressure,preferably a reduced pressure of l to mm. Hg.

The surface active agent of the present invention has severalpredominant characteristics; first, it exhibits heatresisting stability.Particularly, in the case where a nonionic surface active agent, whichis used as raw material, has saturated alkyl group and does not containamino or amide group and contains 1 to mols of either ethylene oxide orboth ethylene oxide and propylene oxide, and Where the higher alcohol,which is used as the raw material, has a saturated alkyl group, theresultant surface active agent exhibits less weight-reduction due tovolatilization and also less change in hue even if it is left in theatmosphere at a high temperature exceeding 200 C. for a long time. Sucha high heat resistance couldnot be expected in conventional surfaceactive agents. Secondly, all of the surface active agent of the presentinvention has remarkably reduced foaming property in comparison withconventional surface active agents.

The surface active agent of the present invention is widely used as anemulsifier, solubilizer, detergent, dispersant, lubricant, antistaticagent, defoaming agent, etc. in the similar manner to that ofconventional sunface active agents. Among the surface active agents ofthe presuses as, for example, an antistatic agent and lubricant forsynthetic fibers which are treated at a high temperature, additive formetal-lubricating oil which has antioxidative property, internalantistatic agent for synthetic molded article or synthetic fiber, andpurifying and dispersing agent for engine oil, etc.

In order that the invention may be more fully under- Y stood, examplesare given below.

EXAMPLE 1 490 g. of poly[8]oxyethylene lauryl ether, which were preparedby adding an average of 8 moles of ethylene oxide to 1 mole ofcommercial lauryl alcohol, 103 g. of triphenyl phosphite and 0.5 g. ofpotassium hydroxide were charged into a four neck flask equipped with anagitator, thermometer and vacuum apparatus. The resultant mixture washeated to 130 C. and stirred for one hour and then, treated under areduced pressure of 10 mm. Hg at a temperature of 130 to 180 C. forthree hours to effect dephenolization. 93 g. of phenol was distilledoff. After filtration, colorless and transparent oily product having aspeeific gravity of 1.014 (ZS/4 C.) was obtained. The resultant productproved that it did not have an infrared absorption spectrumcorresponding to an OH product was tested as will be described later.

A numerical value within the brackets indicates an average number ofmoles of ethylene oxide added to the conventional surface active agent.

EXAMPLE 2 group. The

980 g. of poly[l5]oxyethylene-poly[2]oxypropylene g 4 hol, 103 g. oftriphenyl phosphite and 0.5 g. of potassium hydroxide were treated inthe same manner as'described in- Example 1 to effect dephenolization. 93g. of phenol was distilled off. After filtration, a white waxy productwas obtained. The product proved that it did not have an infraredabsorption spectrum corresponding to an OH group. The product was testedas will be described later.

EXAMPLE 3 162 g. poly[9]oxyethylene lauryl ether, 138 g. of tri-(o-chlorophenyl) phosphite and 0.2 g. of sodium hydroxide were chargedinto a four neck flask equipped with an agitator, thermometer and vacuumapparatus. The mixture was heated to C. and then treated at atemperature from 130 to 180 C. .under a reduced pressure of 5 mm. Hg fortwo hours to effect dephenolization and to distill off 42 g. ofo-chlorophenol. Further, 126' g. of commercial lauryl alcohol were addedto the above product. Then, the mixture was treated at a temperaturefrom 180 to 250 C. under a reduced pressure of 5 mm. Hg for 4 hours toeffect dephenolization. 84 g. of o-chlorophenol were distilled off.After filtration, colorless and transparent oily product having aspecific gravity of 0.952 (25/ 4 C.) was obtained. The resultant productproved that it did not exhibit an infrared absorption spectrumcorresponding to an OH group. The product was also tested as will bedescribed Methods similar to those described in Examples 1 to 3 wererepeated except that starting materials and reacting conditions were aslisted in Table l and Table 2, respectively.

OH group. They were tested as will. be described later.

TABLE 1 Ex. Nonionic surfactant Ph No. Higher alcohol G. este r i G. 4.Poly[8]oxyethy1ene 00!; l 560 Tri hl h phenol ether. y phii ph ii i enyl138 5- Polylaloxypropylenepoly[10] 834 .....do 138 orgethylene nonylphenol e er. I

6. Poly[10]oxyethylene oleyl 708 Trl-p-cresyl phos- 119 ether. phlte. 7.Polt3lr1[15]oxyethylenecetyl Y 902 .....do 119 Y a e er. 8..-..Polyl2loxyethy1ene non l 308 Ti-o-cre 1 l1" I v phenol ether. y qphite. 9. Poly[18]oxyethylene trl-ethyl 1,199 .....do .119

benzene phenol ether. v 10--.- Poly[10]oxyethylene lauric I 654'I'rl-butylphenyl am ester. 1 a phosphite. v, 11-Polyl3loxypropylene-polylQ] 710 ..-Ld0......'.'.-..-.-.'.

otxlyethylene butylphenol e er. 12- Poly[l0]oxyethylene hexa- 681'Iri-phenyl phos- 103 decylamjne. phite. 13-... Poly[10]oxyethylenestearie 1722 -..-.do 103 acid amide. 14- Po1y[60]oxyethylene nonyl-2,860 103 1 plhenol ether. 15 gggi 0157] 'lrl-o-chlorophenyl 138 Lam-y]alcohol; p "I i i 16 Poalggllilgoxyethylenelauryl 208 w t lphenyl 135 fli% 1------,;----=...-.- 87 PMSPM- o y oxyet lene oct 1- 395 I phenolether. y 135 Decanol I 53 18 Poly[10]oxyethylene-poly[5 338 oxypropylenestearyl ether.

gtearlgll alcoh olim 187 oy oxye yeneol 4 261 i 19- i opylenelaurib e eid Tn'phenyl phosl 103 T amide. phite. p auryl alcohol 262"'{P0lt[6]oxyethylene lauryl 296 103 e er. Lauryl alcohol 60Poly[6]oxyethylene oleyl ether. 354 m3 glelsylzzallcoholifiul 90 0y oxyeene di-non l- 818 phenol ether. y 103 Myrlstyl alcohol 57 All of theresultant products proved that they did not"- have an infraredabsorption spectrum corresponding to an TABLE 2 Amount of phenolicReaction oompd. distilled Temp. Time ofi(g.) 0.) (hr.) Catalyst G.Appearance oiproduct Example No.

0. 2 Pale yellow and transparent oily. 0. 4 Colorless and transparentoily. 0. 3 Pale yellow and transparent oily. 8 NaOlight of the prodof 30parts by 0.3 Pale yellow waxy.

(2) Emulsification At 220 C. for hr.

Decrement by volatilization (percent by weight) Each of the mixtures ofparts by we net in Example 1 and parts by weight of refined mineral oilhaving a viscosity of sec., weight of the product in Example 15 and 70parts by given in weight of refined mineral oil having a viscosity of100 30 sec., and of 30 parts by weight of the product in Example 20 and70 parts by weight of refined mineral oil having Heat-resistingstability At 220 C, for 1 hr.

Decrement by volatili- (p Hue weight) change stability Properties of theproducts obtained in the above Ex- TABLE 3 Testing items Foaming prop-(dyne/cm.) erty (mm.)

Immedi- 3 min; ately after after Hue 1% 0.5% dripping dripping changeProperties of the surface active agent of the present tion ishereinafter described.

(1) Surface tension, foaming property and heat-resisting Surface tensionv i i 0 n t I w m w v 0 v m m v n t n p t n 0 m 0 m m o t t t n M n m Mn m p. m t .p. m 8 S a 0 m 8 D m n. n as P w a m aye". m B u m n mam u 0m a n a my Y i m. mum hwhw n ls s SHUWS... 1. .SV 90 OOOM OBX m tmDDD eD t a m d mm m M C PWC YPYP 0% 55338559551559% 0 0 0 0 00 0 0 &0 00 0 &n rm u n n u u u n n Tm u u n n n n r .r u u .v. .m u n n n u "m n e :mmm u n m "awa t: "we .tt e m .tH .68 H mArHHmHHm Hmm Oaa MOOaOO aOaa KNNTKKNKKKNKNN 54333344332708 3 1 0000000000 000 mmwwmmwwwmmwmmm 11111111111 11 778888443337444 220000229992222 11111111 1111 n u 4 amples 1to 22 were determined. Results are Table 3 in comparison withconventional surface active agents.

inven Surfactants 3894678385255599621949 alzLnmomLLlfiz mkfiiamzamiLamnmnnnnncnnnnnocsccnnnnfln 3082377355 18161744487 LLL10 0 0 0 0 2 L0 &2 2LL2LLQ 1.-.-..-..---.---.- S 165 c r 1 Control surface active agents areas follows: 1 poly[8]oxyethylene lauryl ether, 2 poly [8]oxyethy1eneoctyl phenol ether, 3=poly[l0]oxyethylene oleyl phenol ether,4=poly[20]oxyethylene sorbitan tristearate, 5=poly[10]oxyethylenestearic acid amide. 9 Surface tension was determined by a Du N oily-typetension meter at 25 C. a Foaming properties were tested by Ross Meilesmethod at 40 C. using 0.25% by weight solution of surfactant. Height offoams were determined immediately after and 3 min. after dripping.

4 Heat-resisting stability was tested by the following method; 30 g. ofeach sample surfactant were charged into a test tube (36 mm. x 200 mm.).Aiter the sam e was left in a thermostat at 220 C. r 6 hours withoutcorking the test tube, decrement of the sample by volatlllzation and huechange of the sample were measured. Marks "n," gfilfiz" and r" designateno change," "slightly changed," changed" and remarkably changed," respecve y.

a viscosity of 100 Saybolt sec. could be uniformly dispersed in water atroom temperature.

In the case where a mixture of 30 parts by weight of the product inExample 6 and 70 parts by weight of butyl stearate was heated to 50 C.and then, 150 parts by weight of warm water at 60 C. were poured intothe heated mixture while being gradually stirred, a uniform emulsion wasobtained.

Further, in the case where a mixture of parts by weight of the productin Example 8 and 50 parts by weight of spindle oil having a viscosity of150 sec. was heated to 80 C. and then, 35 parts by weight of warm waterat 80 C. were gradually poured into the heated mixture while beingstirred, a uniform and stable emulsion of w/o type was obtained.

Still further, in the case where 2 g. of the product in Example 14 wasdissolved in 30 g. of water and then, 70 g. of commercial gasoline wasdripped for min. while being violently stirred, a highly viscousemulsion having a viscosity of 20,000 cps. at 20 C. was obtained. Theresultant emulsion was found to be useful for printing.

(3) Detergency As to the products in Examples 1, 4, 5, 10 and 17,detergency was tested by a detergency testing procedure determined bythe Japan Oil Chemists Society using a Launder- O-Meter under thefollowing conditions; temperature, 40i1 C.; time, 30 min.; 20 steelballs each having a diameter of M4 inch were used; number ofrevolutions, 40 r.p.m.; concentration of surfactant, 0.3% by weight.Spectral reflectance was determined by a spectrophotometer made byHitachi Seisakusho, Japan, wherein a meas ured value of magnesiumcarbonate specimen was 100 in relation to the standard value. Detergencyefficiency was calculated from the following equation:

Detergency efficiency (percent) 55 X 100 where;

D=Detergency efliciency of deterged fabric,

S=Detergency efficiency of stained fabric,

O=Detergency efficiency of original fabric. Results are given in Table4.

TABLE 4 Detergency Surfactant efliciency Product in Example:

(4) Antistatic property to pick-up OWF, the taffeta was air-dried.-Anti'static property of the resultant taffeta was measured-by a Tex- II and TABLE 5 Surface electric resistance (ohm) Nylon Surfactant Productin Example:

Tetoron Further as to the products in Examples 1-3, 13, 18, 19 and 20,antistatic property was tested by the following method:

0.2 g. of each product was added to g. of polyethylene ("Sumikasen L-702made by Sumitomo Chemical, Japan) and the mixture was roll-milled at C.for 10 min. and then, subjected to press molding at C. for 10 min. toform a sheet having a thickness of 2 mm.

When the resultant sheet was superposed above the ash of cigarette at adistance of 1 cm. after it was rubbed with nylon cloth ten times, theash was not attracted to the sheet, resulting in proof that the sheetcontained a favorable antistatic property. On the other hand, in thecase of the sheet which did not contain the product, the ash wasattracted to it.

Color of both sheets did not change through the above press moulding.

What we claim is:

1. A surface active compound having the formula R1O\ RzO-P wherein R Rand R are each the same residue of a nonionic surface active compound,said residue having a formula selected from a member of the groupconsisting of wherein in each of said formulas, n is an integer of 1 to20.

2. A surface active compound according to claim 1 wherein each of R Rand 3 is represented by the formula C EH11 wherein n is an integer of 1to 20.

3. A surface active compound according to claim 1 wherein each of R Rand R is represented by the wherein each of R R and R is represented bythe forformula mula CnHro 5 @mmmon-cm.

-O(C3H40) r-CzHrwherein n is an integer of 1 to 20.

wherein n is an integer of 1 to 20.

4. A surface active compound according to claim 1 wherein each of R Rand R is represented by the for- 10 References Cited UNITED STATESPATENTS mula 2,361,022 10/ 1944 Gilbert 260-403 c H 2,987,385 6/1961 DeGray 44-66 3,004,057 10/ 1961 Nunn, Jr 260-461 O (CIHO)H CZH V V 153,682,988 8 /1972 Lewls 260-403 C H ELBERT L. ROBERTS, Primary ExaminerUS. Cl. X.R.

wherein n is an integer of 1 to 20.

5. A surface active compound according to claim 1 25232.5, 351; 260-950,951, 944

